DE10392702B4 - Electrically conductive fluid distribution element with electrically conductive coating, method for its production and fuel cells with the fluid distribution element - Google Patents

Abstract

A method of manufacturing an electrically conductive fluid distribution element comprising the steps of:
a substrate is provided;
the substrate is cleaned with an ion beam; and
depositing an electrically conductive coating on the substrate by PVD to a thickness of less than 100 nm,
wherein the cleaning and the deposition are carried out substantially simultaneously.

Description

FIELD OF THE INVENTION

The The present invention relates to fuel cells and more particularly electrically conductive fluid distribution elements and their production for such fuel cells.

BACKGROUND OF THE INVENTION

Fuel cells have been proposed as a power source for electric vehicles and other applications. A known fuel cell is the proton exchange membrane (PEM) fuel cell, which comprises a so-called "membrane electrode assembly" comprising a thin solid polymer membrane electrolyte having an anode on one side of the membrane electrolyte and a cathode on the opposite side of the membrane electrolyte. The membrane electrode assembly is sandwiched between a pair of electrically conductive fluid distribution elements that serve as current collectors for the anode and cathode. Flow fields or gas distributor fields are provided for distributing the gaseous reactants of the fuel cell over the surfaces of the respective anode and cathode. The electrically conductive fluid distribution elements may themselves form part of the flow field in the form of suitable channels and openings therein for distributing the gaseous reactants of the fuel cell (ie, H ₂ and O ₂ ) across the surfaces of the respective anode and cathode.

One Fuel cell stack includes a plurality of in electrical Row of stacked membrane electrode assemblies. The membrane electrode assemblies are separated from each other by the impermeable, electrically conductive Fluid distribution elements separated, which also as bipolar plates or Bipolar plates are known. The bipolar plate has two major surfaces, from one to the anode of one cell and the other to the surface Cathode of the next has adjacent cell in the stack. The plate conducts electrical Electricity between the neighboring cells. Contact elements at the ends of the stack are only in contact with the end cells and therefore become referred to as end plates.

In a PEM fuel cell environment using H ₂ and O ₂ (optionally air), the bipolar plates and other contact elements (eg, end plates) are in constant contact with acid solutions (pH 3-5) and operate at elevated temperatures of the order of 60 degrees Celsius to 100 degrees Celsius. Moreover, the cathode operates in a highly oxidizing environment while exposed to compressed air. The anode is consistently exposed to a harsh environment of pressurized hydrogen. Therefore, many of the conventional contact elements are made of metal and must be resistant to acids, oxidation as well as hydrogen embrittlement in the fuel cell environment. However, metals that meet these criteria are expensive.

Light metals, such as aluminum and titanium and their alloys, such as stainless steel is also more bipolar for use in manufacturing Plates of fuel cells have been proposed. Such metals are more conductive and can in very thin Plates are formed. Unfortunately Such light metals are susceptible to corrosion in the harsh fuel cell environment, and made of it loosen bipolar plates either (for example in the case of aluminum) or form Passivation oxide films with high electrical resistance on their Surface (for example in the case of titanium, stainless steel and aluminum) containing the Internal resistance of the fuel cell increases and reduces their efficiency. To solve this problem, has been proposed, the bipolar plates made of light metal to coat with a combination of layers that are both electric conductive as well as corrosion resistant are to thereby protect the underlying metal. Please refer For example, Li et al., RE 37,284 E assigned to the assignee of transmitted to the present invention is.

These however, sheet-like coatings are expensive due to the thickness, which must be deposited on the plates to prevent them from corrosion protect. Another disadvantage is that the properties These thick layers degrade while exposed to high stack compression pressures which reduces corrosion resistance.

From the DE 100 58 337 A1 For example, it is known to use a sheet metal product that can be used, in particular, as a bipolar plate in a fuel cell, that has on at least one side a conductive and corrosion-resistant protective coating of a metal oxide.

In the WO 00/590551 A2 discloses a component, such as a pole plate or a Zellrah men for a fuel cell, which has a noble metal coating on at least one location and / or side, wherein the average thickness of the noble metal coating is 0.1 microns and the precious metal coating discrete conduction paths and / or pipeline islands.

From the WO 02/27838 A2 For example, a proton exchange membrane type fuel cell is known which comprises a fluid distribution element which made of plastic, stainless steel, nickel foam and the like with a noble metal coating having a thickness of 0.5 to 2 μm applied thereto.

It There is therefore a need for a bipolar plate that is light and cost-effective can be made, which is resistant to corrosion, as well as a high Degree of conductivity has.

SUMMARY OF THE INVENTION

The The present invention provides an electrically conductive fluid distribution element for a fuel cell vor, which is an electrically conductive substrate having a first and second main surface, a flow field on the first surface for distributing fluid along the first surface and an electrically conductive one Coating on the first surface comprises, which comprises a noble metal or a compound containing a noble metal. Here, the precious metal of Ru, Rh, Pd, Ag, Ir, Pt and Os and preferably from Au as well as their mixtures are selected.

The Coating is relatively thin and has a thickness of less than 100 nm, better less than 80 nm, more preferably less than 50 nm, preferably 20 nm and is most preferably in a range of 10 to 20 nm. The coating is also preferably relatively smooth when supported by ion beam assisted PVD (physical vapor deposition, physical vapor deposition) is applied.

The The present invention also provides a method of ion beam assisted PVD for coating the electrically conductive fluid distribution element with the conductive coating of precious metal and a fluid distribution element according to the invention fuel cell.

Further Areas of application of the present invention are more detailed below described. It should be understood that the detailed description as well as the specific examples, while being the preferred embodiment specify the invention, for illustrative purposes only and are not intended to limit the scope of the invention.

BRIEF DESCRIPTION OF THE DRAWINGS

The The present invention will now be described by way of example only to the accompanying drawings, in which:

1 a schematic exploded view of a PEM fuel cell stack (there are only two cells shown);

2 Figure 11 is an exploded view of an exemplary electrically conductive fluid distribution element that may be used with PEM fuel cell stacks;

3 a sectional view in the direction of 3-3 of 2 is;

4 an enlarged portion of the bipolar plate of 3 is;

5 Fig. 10 is a partial section of a bipolar plate having a thin substrate with foamed metal flow fields mounted on both sides thereof;

6a a partial section of a bipolar plate as in 5 is, wherein the inner and outer surfaces of the foam are coated with an electrically conductive material;

6b a partial section of a bipolar plate as in 5 in which only the outer surfaces of the foam are coated with an electrically conductive material;

7 is a partial section of a bipolar plate, which consists of a composite of electrically conductive particles which are distributed in a binder matrix coated with an electrically conductive material;

8a is a partial section of a bipolar plate consisting of a composite comprising continuously conductive particles dispersed in a bovine matrix;

8b a partial section of a bipolar plate as in 8a is coated with an electrically conductive material;

9 Figure 12 is an illustration of an ion beam assisted PVD apparatus used to coat the bipolar plates with the electrically conductive material;

10a and 10b Show comparisons of coatings made by a process of ion beam assisted PVD as well as by a galvanic process;

11a and 11b Atomic force microscopy images as well as roughness analyzes are comparing coatings made by a process for ion beam assisted PVD as well as a plating process;

12 Figure 12 is a graph showing a contact resistance caused by the electrically conductive coating of the present invention as well achieved by a coating according to the prior art;

13 Fig. 12 is a polarizing graph showing a cell voltage versus a current density and a contact resistance obtained by an electroconductive stainless steel coating of the present invention as compared with an uncoated stainless steel substrate as well as poco-graphite;

14 is a graph showing corrosion currents while the potential was cyclically changed between +0.4 and +0.6 V (vs. Ag / AgCl) in a vented solution at 80 degrees Celsius; and

15 Figure 12 is a graph showing a potentiostatic transition of a stainless steel sample coated with 10 nm gold at an applied potential of +0.6 V (Ag / AgCl) in a vented simulated fuel cell solution operating at 80 degrees Celsius has been.

DETAILED DESCRIPTION THE PREFERRED EMBODIMENTS

The The following description of the preferred embodiments is merely exemplary nature and not intended to the invention, their Application or their use.

1 shows a bipolar fuel cell stack 2 with two cells and with a pair of membrane electrode assemblies (MEAs) 4 and 6 separated from each other by an electrically conductive fluid distribution element 8th are separated, the following as a bipolar plate or bipolar plate 8th is designated. The MEAs 4 and 6 as well as the bipolar plate 8th are together between stainless steel clamp plates or end plates 10 and 12 and end contact elements 14 and 16 stacked. The end contact elements 14 and 16 as well as both working sides of the bipolar plate 8th include a plurality of grooves or channels 18 . 20 . 22 respectively. 24 for distributing fuel and oxidant gases (ie, H ₂ and O ₂ ) to the MEAs 4 and 6 , Non-conductive seals 26 . 28 . 30 and 32 provide seals as well as electrical insulation between the various components of the fuel cell stack. Gas permeable conductive materials typically include carbon / graphite diffusion papers 34 . 36 . 38 , and 40 attached to the electrode sides of the MEAs 4 and 6 be pressed. The end contact elements 14 and 16 are added to the carbon / graphite papers 34 respectively. 40 pressed while the bipolar plate 8th to the carbon / graphite paper 36 on the anode side of the MEA 4 and to the carbon / graphite paper 38 on the cathode side of the MEA 6 is pressed. Oxygen is delivered to the cathode side of the fuel cell stack from a storage tank 46 via a suitable supply piping 42 while delivering hydrogen to the anode side of the fuel cell from a storage tank 48 via a suitable supply piping 44 is delivered. Alternatively, ambient air may be supplied to the cathode side as an oxygen source and hydrogen to the anode from a methanol or gasoline reformer or the like. It is also a discharge tubing (not shown) for both the H ₂ and O ₂ sides of the MEAs 4 and 6 intended. An additional piping 50 . 52 and 54 is for supplying liquid coolant to the bipolar plate 8th and the end plates 14 and 16 intended. A suitable piping for the discharge of coolant from the bipolar plate 8th and the endplates 14 and 16 is also provided, but not shown.

2 is an exploded view of an exemplary bipolar plate 56 which can be used according to a first embodiment of the present invention. The bipolar plate 56 includes a first outer metal layer 58 , a second outer metal layer 60 and an inner clearance metal layer 62 between the first metal layer 58 and the second metal layer 60 , The outer metal layers 58 and 60 are formed as thin as possible and are formed by punching or other conventional method of forming sheet-like metal or sheet metal. The outer layer 58 has a first work page 59 on its outside, which faces a membrane electrode assembly (not shown), and is configured to form a flow field 57 is provided. The flow field 57 is through a variety of jetties 64 defines, in between a multitude of grooves 66 defining the "flow field" through which the reactant gases of the fuel cell (ie, H ₂ or O ₂ ) travel in a meandering path from one side 68 the bipolar plate to its other side 70 stream. When the fuel cell is completely assembled, the webs become 64 to the porous material, namely the carbon / graphite papers 36 or 38 , pressed, in turn, to the MEAs 4 and 6 be pressed. For simplicity's sake 2 only two groups of bars and grooves. In fact, the lands and grooves cover the entire outside of the metal layers 58 and 60 that with the carbon / graphite papers 36 and 38 engage. The reactant gas is at grooves 66 from a distributor 72 delivered along one side 68 the fuel cell is arranged, and leaves the grooves 66 via another distributor 74 that is adjacent to the opposite side 70 the fuel cell is arranged. How best in 3 can be seen, includes the bottom of the location 58 a variety of ribs 76 , which in between a variety of channels 78 define, by the coolant during operation of the fuel cell is flowing. As in 3 can be seen, lies under each jetty 64 a coolant channel 78 while under each reactant gas groove 66 a rib 76 lies. Alternatively, the location could be 58 be formed flat and the flow field be formed in a separate layer of material.

The metal layer 60 is similar to the situation 58 , The inside 61 the situation 60 is in 2 shown. In this regard, a variety of ribs 80 shown in between a variety of channels 82 define, by the coolant from one side 69 the bipolar plate to the other 71 flows. Similar to the blackboard 58 , and how best in 3 can be seen owns the outside of the location 60 a work page 63 , The location 60 is designed to be a flow field 65 is provided. The flow field 65 is through a variety of webs 84 Defined by a variety of grooves 86 define which the flow field 65 through which the reactant gases flow. An inner metal spacer layer 62 is between the outer layers 58 and 60 positioned and includes a plurality of openings 88 in order to allow coolant between the channels 82 in a position 60 and the channels 78 in a position 58 can flow, whereby laminar boundary layers are broken and a turbulence is caused, which is a heat transfer with the insides 90 and 92 the outer layers 58 respectively. 60 increases. Thus, the channels form 78 and 82 respective coolant flow fields at the through the layers 58 and 60 defined internal volume.

4 is an enlarged view of a section of 3 and shows the ribs 76 at the first location 58 and the ribs 80 at the second location 60 by a binder 85 with the distance position 62 are connected.

According to the present invention, and as best in 4 can be seen, are the work pages 59 and 63 the bipolar plate with an electrically conductive, oxidation-resistant as well as acid-resistant coating 94 which comprises a noble metal selected from the group consisting of Ru, Rh, Pd, Ag, Ir, Au, Pt and Os. The preferred coating is gold (Au). The thickness of the coating 94 is less than 80 nm, preferably less than 50 nm, and most preferably 10 to 20 nm. Optionally, the insides 90 and 92 the layers 58 and 60 also with a coating 94 be covered (not shown).

Another possibility is just the bars 64 . 84 and not the grooves 66 . 86 the layers 58 respectively. 60 to coat. Thus, only adjacent electrically conductive surfaces are coated in contact with each other.

In a first embodiment, one includes the layers 58 and 60 forming metal substrate is a corrosion-prone metal, such as aluminum, titanium or stainless steel. The coating 94 gets directly to the layers 58 and 60 applied.

In a second embodiment is in 5 a sectional view of another electrically conductive fluid distribution element 100 shown. The element 100 is with a thin substrate layer 102 built up, the foamed flow fields 106 has. This bipolar plate has a thin barrier layer 102 preferably consisting of a solid titanium metal layer, wherein foam 106 (about one-half to about 3 millimeters thick) by welding or brazing on both sides. The location 102 forms the gas barrier, and the foam 106 forms the fluid flow fields. As you can see, the foam has 106 opposite main surfaces 110 and 111 , The foam 106 has a main surface 110 leading to the metal layer 102 points, and another major surface 111 across from 110 , Typically, the main surface faces 111 to the MEA. As in the 5 and 6 can be seen forms the main surface 111 the outer surface of the electrically conductive element 100 , Foams can be made as metal foams or carbon based foams. Metals that can be made as a solid foam include copper, aluminum, nickel, titanium, silver, and stainless steel, with the preferred metals being nickel and stainless steel. A variety of foamed metals are available from AstroMet, based in Cincinnati, Ohio. Processes for producing these metal foams are in the U.S. Patent No. 4,973,358 described. Carbon based foams are available from Ultra Met. In one aspect, the noble metal coating becomes 94 on the location 102 applied, as in 5 you can see.

In other aspects of the second embodiment, the coating varies 94 of the substrate 102 and the foam 106 depending on their respective properties. Depending on the construction material as well as the arrangement of the substrate 102 and the foam 106 It may be suitable for all surfaces of the substrate 102 to coat if a metal layer is used. In the case of metal foams, it is possible to use all the internal and external surfaces of the foam 106 to coat or it is possible to coat only some of the surfaces. It should be noted that the foam described here 106 is an open cell foam. This shows that continuous flow paths or channels through the foam 106 present through interconnected openings or pores, which are defined by the thickness of the foam 106 through each other are open. The outer surfaces 109 of the foam 106 refer to the aforementioned major surfaces, such as 110 and 111 , by Surface pores formed openings include. The interior surfaces of the foam are surfaces that pass through the internal openings or pores 108 be formed as in 5 is shown.

In one aspect of the second embodiment, it is possible to have all the internal openings 108 and all external surfaces 109 of the foam 106 leading to the MEA and to the planar substrate layer 102 to coat. ( 6a ) If a chemically unstable foam 106 , such as aluminum or nickel is used, this is advantageous. Optional are the surfaces of the board 102 coated. If a chemical more stable foam 106 As used, for example, of stainless steel, the coating of the inner and outer surfaces of the foam 106 depending on the environment of the cells is not necessary. In this case, the foam interior may remain uncoated or coated to a given depth. The coating is preferred 94 on the parts of the foam 106 applied, the electrons from one medium to the next, for example from the foam surface 111 to the MEA or foam surface 110 to the planar position 102 to transfer. As in this embodiment ( 6b ), the coating becomes visible 94 on the electrical conductive element 100 applied, in which electrons in and out of the structure of the electrically conductive element 100 flow. Once electrons go through the structure of the element 100 flow, ie the foam 106 , there is no resistance in the foam 106 , and the next adjacent resistance area is only encountered when the electrons foam 106 towards or at the surface of the metal layer 102 leave. In this embodiment, the coating is 94 on the main surface 111 of the foam 106 to a depth level of less than 80 nm, preferably less than 50 nm, and most preferably applied to a depth level of 10-20 nm. In addition, it is desirable in this embodiment, also the foam 106 to a depth level of 10-20 nm at the major surface 110 to coat, at which he to the planar sheet metal layer 102 has.

In a third embodiment, as in 7 can be seen, the electrically conductive coating 94 to another electrically conductive fluid distribution element 112 be deposited, which is a polymeric material 113 with a conductive fibrous filler 114 comprising an orientation through the plane, which provides a conductivity path through the element. This is a composite material. The polymer material 113 is preferably a suitable thermosetting or thermoset polymer, and more preferably selected from the group of materials comprising: silicone, polyisobutylene, epoxy, vinyl esters, and phenolic or phenolic resin, respectively. Alternatively, the polymer material 113 preferably a suitable thermoplastic and is more preferably selected from the group of materials comprising: polypropylene, ethylene tetrafluoroethylene (ETFE), nylon as well as rubber-modified polypropylene. While the foregoing thermosetting and thermoplastic polymers containing a conductive fibrous filler are presently preferred, it will be apparent to those skilled in the art that other specific materials may also be suitably imparted to the particular detail specification of an application. For example, an electrically conductive polymer such as polyacetylene may be used which does not require a conductive fibrous filler.

According to the third embodiment ( 7 ) comprises the conductive fibrous filler 114 a fiber material having an aspect ratio (ie, the length to thickness ratio) greater than about 5: 1, and has good electrical conductivity properties as well as good thermal conductivity properties. In this regard, the preferred conductive fiber materials currently include carbon fibers (such as pitch based fibers, PAN based fibers or others), graphite fibers, metal coated graphite fibers (such as gold coated fibers) and various metal fibers comprising stainless steel fibers. While the fibrous conductive filler 114 Generally, having an aspect ratio of greater than 5: 1, the conductive fibers more preferably have an aspect ratio greater than 10: 1, and most preferably have an aspect ratio greater than 15: 1.

In addition to the polymer material 113 and the conductive fibrous filler 114 For example, the composite of the present invention may optionally contain a nonconductive fibrous material in an amount of 1 to 10% by volume to increase the mechanical properties of the composite. As presently preferred, the nonconductive fibrous filler may be selected from the group comprising glass fibers. Likewise, the composite material may comprise a conductive non-fibrous material of up to 10% by volume. As presently preferred, the conductive non-fibrous material may preferably be selected from the group comprising carbon black, graphite powder, and metal-based powders. Examples can be taken from the prior art, see for example the U.S. Patent Nos. 6,096,450 A 6,103,413 A and 6,248,467 A In this embodiment ( 7 ), the metal coating facilitates the electrical conductivity of the composite material to the next adjacent element of the fuel cell.

In a fourth embodiment, incorporated in the 8a and 8b As shown, the electrically conductive fluid distribution element that may be used is a polymeric bipolar plate 116 , the one Variety of electrically conductive fibers 118 which are arranged in a polymer body portion, wherein each fiber 118 continuously from the first surface 120 of the polymer body portion to the second surface 122 of the polymeric body portion extends in an orientation through the plane.

The main body section 124 is formed of a relatively high strength polymeric material, suitable thermal properties, as well as low permeability to coolant fluid and reactant gases. Preferably, the main body portion 124 formed of a solidified thermally conductive polymer, such as carbon-filled epoxy or epoxy resin. However, the main body portion 124 be formed of other suitable materials having such desired properties. For example, the main body portion 124 made of silicone, polyisobutylene, polyvinyl ester, polyester, phenol or phenolic resin, polypropylene, ETFE, nylon or rubber-modified polypropylene. The thermal conductivity can be increased by loading the polymer material with the carbon, graphite or noble metal particles.

The tubular elements 128 located in the main body section 124 the bipolar plate 116 serve to define a secondary flow field therethrough to direct a cooling fluid through the Separatorplatte and thus to control its heat energy. The tubular elements 126 are designed so that a cooling fluid through a piping 70 is performed to remove heat energy from the fuel cell stack or add heat energy to the fuel cell stack. The coolant headers, which are the tubular element 126 To fluidly couple with the tubing should provide electrical insulation therebetween to provide a shunt current between the fibers 118 and the tubular elements 126 to prevent.

As presently preferred, the tubular elements are 126 made of carbon filled polymer. It should be noted, however, that the tubular elements 126 can be made of any of a variety of materials that are thermally conductive and not susceptible to corrosion in an environment of the gaseous reactant or the refrigerants commonly used in a fuel cell stack. Some other suitable materials include titanium, carbon or stainless steel.

The guiding elements 118 positioned in the separator plate are generally oriented in an orientation through the plane and extend continuously from the top surface 128 the separator plate to the lower surface 130 the separator plate to minimize the sheet resistance of the plate, as in 8a is shown. Each conductive element 118 is an elongated fiber (ie with an aspect ratio of 2000: 1 or greater). As in 8a can be seen is the first end 132 on the upper surface 128 exposed, and the second end 134 is on the bottom surface 130 exposed.

As in 8b The conductive coating is visible 94 on the polymeric bipolar plate 116 been deposited so that the conductive elements 118 with the conductive coating 94 stay in contact. The guiding elements 118 are formed of carbon-based electrically conductive fibers such as pitch-based fibers, PAN-based fibers, or other fibers. The guiding elements 118 may also be formed of other suitable electrically conductive fibrous materials, such as graphite fibers, Au-coated graphite fibers, Pt-coated graphite fibers, Au fibers, Pt fibers, or coated stainless steel fibers. In the 8A and 8B boost those in conjunction with the conductive coating 94 used conductive elements 118 an electrical conductivity between adjacent bipolar plates.

It It is obvious that the application of a conductive coating on any combination of surfaces of a foam or one Planar situation possible is, and further, that a coating of the foam on any desired extent its thickness also possible is. It is also obvious that in the case of composite or Fiber material the metal coating the electrical conductivity increases or at least relieves.

Now, referring to 9 a method for depositing the conductive coating 94 on the bipolar plates of the above-mentioned four embodiments. To the conductive coating 94 depositing on the substrate, a method of internally assisted PVD is used.

As in 9 is seen, becomes a device 136 used for internally supported PVD. The device 136 includes a deposition chamber 138 and two electron guns and electron guns A and B for depositing the metal coating. The device 136 also includes a low energy ion source or gun used to sputter clean the substrates, as well as a turbo pump that allows the device to operate in an ultra-high vacuum.

That through the conductive coating 94 to Coating substrate is in the deposition chamber 138 arranged. Once the substrate in the chamber 138 is placed, the pressure is lowered to about 0.0133 N / m ² (about 10 ^-4 Torr). A first pot 140 in the chamber contains the precious metal to be deposited. When a combination of metals or precious metals is to be deposited, a second metal is placed in a second crucible 142 intended. For example, there is a crucible 140 containing titanium, which is to be deposited as a first layer, and a crucible 142 , the gold to be deposited as a second layer over the titanium does not fall outside the scope of the present invention. Another option available may be to deposit a combination of metals simultaneously.

A Ion gun is used to sputter clean the substrate. When the ion gun sputters the substrate clean, it becomes an electron beam used to melt and vaporize the precious metals. The precious metals are then deposited on the substrate at a rate of 0.10 nm / s deposited to a thickness of less than 80 nm by Dick monitoring devices is observed.

An important aspect of the internally assisted PVD method is that the sputter cleaning of the substrate and the application of the conductive coating occur substantially simultaneously. By simultaneously sputter cleaning and coating of the substrate, the conductive coating 94 are deposited on the substrate with ultra-thin thicknesses of less than 80 nm, preferably less than 50 nm, and most preferably between 10 and 20 nm. If the conductive coating 94 has a thickness of 10-20 nm, the conductive coating preferably has a loading of 0.02-0.04 mg / cm ² .

The present process is an improvement over sequential cleaning and deposition. When the substrate used is a metal substrate, such as titanium or stainless steel, an oxide film forms in the time between the on-going cleaning and the deposition of the metal on the substrate via PVD. By simultaneously cleaning the substrate and depositing the noble metal, the oxide layer is completely and continuously removed, thereby preventing or at least substantially reducing oxide formation or other damage to the surface. The concurrent cleaning of the substrate and deposition of the noble metal can be achieved due to the fact that the ion energies required to remove the oxide layer are low. Since the ion energies are low, the bombarding ion fluxes are generally smaller than the deposition atom fluxes emitted by the electron guns A and B. This is because the oxides that are removed are lighter than the metal on the substrate as a conductive coating 94 is deposited. Thus, the low energy ion gun removes only the oxide layer and not the conductive coating 94 , The result is that a coating 94 of metal with an excellent adhesion to the substrate is deposited. Further, it is possible to coat only a very thin layer on the order of 10-20 nm, thereby achieving good surface coverage, relatively uniform coverage as well as good adhesion. Thus, the use of internally assisted PVD allows the precious metal to be deposited on the substrate very smoothly, uniformly, and in a thin layer.

It Let it be understood that an important feature of the invention is the deposition a metal coating on a substantially clean surface. In a preferred aspect, a surface cleaning of the substrate via ion gun begun just before the metal deposition is initiated. Then be the cleaning as well as the metal deposition continued simultaneously to complete the deposition process.

As described above, the adhesion of the coating is greatly enhanced by depositing the metal coating on a clean surface, thus resisting delamination from the substrate. For example, when a cathodic current in the range of 10 mA / cm ² -50 mA / cm ² in a solution of 0.5 MH ₂ SO _{4 is applied} cyclically to a coating, hydrogen gas (H ₂ ) is developed As a result of the prior art, these peeled off from the substrate or detached from the substrate. However, when the coating is deposited by the internally assisted PVD process of the present invention, the excellent adhesion of the coating to the clean surface of the substrate resists delamination from the substrate caused by the evolved H ₂ when the cathodic current is applied ,

It should be understood that the use of internally assisted PVD is an improvement over previous deposition techniques, such as sputtering of Au. This is due to the fact that the control of the plasma occurs randomly during sputtering, since the direction, energy as well as the ion flux that occurs on the substrate can not be regulated. In contrast, the internally assisted PVD provides independent control of the deposition parameters Because of the fact that the ion beams used in the ion-assisted PVD have low energy, as well as being well-parallel, divergence angles being only a few degrees.

following Be detailed experimental details regarding a preferred embodiment of the present invention. In this preferred embodiment Gold is selected as the precious metal that is on a substrate Made of 316L stainless steel deposited by internally assisted PVD should.

at In a first series of experiments, gold was deposited on substrates stainless steel by electron beam evaporation in an ultrahigh vacuum deposited. The stainless steel substrates were used an ultrasonic bath first with acetone and then with methanol over each Cleaned for 15 minutes. It turned out that the gold coating had a very bad attachment.

at In a second series of experiments, the substrate was made of stainless steel Steel sandblasted and then using the ultrasonic bath with acetone and then Methanol was purified before depositing gold on the substrate. Although the adhesion was improved, the coating failed, when she was in a corrosion test solution was brought.

at In a third series of experiments, the substrate was made of stainless steel Steel is electrochemically cleaned before it is in the ultrasonic bath from acetone and then Methanol was arranged. Again, the attachment of the gold was improved, however, the coating failed when placed in a corrosion test solution has been.

In a fourth series of experiments, the internally assisted PVD method of the present invention was used. The ion gun used was a 100 to 500 eV Ar ⁺ beam with a current density of 1 to 20 mA / cm ² for 2 to 10 minutes. The evaporation source material was 99.99% pure gold from Johnson-Matthey. The 316L stainless steel substrates used were 25.4 mm x 25.4 mm (1 "x 1") wafers which were first cleaned in an ultrasonic bath of acetone and then methanol for 15 minutes each. The stainless steel substrates were then loaded into the deposition chamber of the internally assisted PVD apparatus and held therein until the pressure was less than 2 × 10 ^-7 Torr 2.67 × 10 ^-5 Pa. The base pressure of the deposition chamber was typically 1.33 × 10 ^-7 Pa in the mid-10 ^-9 Torr range and was always lower than 1 × 10 ^-8 Torr 1.33 × 10 ^-6 Pa. When the ion gun cleaned the stainless steel substrate, a gold plating was deposited with the single electron beam evaporation source at a rate of 0.10 nm / s at a temperature of 35 degrees Celsius to 40 degrees Celsius. The gold coatings showed excellent adhesion even after being placed in a corrosion test solution for nearly 100 hours.

in the Comparison to deposition techniques of the prior art, such as for example galvanic processes, The present invention provides significant advantages. For example is the deposition of precious metals by electroplating on one Substrate very expensive. This is due to the fact that a thick coating of about 100 nm or more is required to prevent corrosion of the substrate when a metal substrate, such as stainless steel, aluminum or titanium used becomes. Further, when the plating is used, the adhesion is of the noble metal on the substrate bad. Therefore, to the attachment To improve, a liner of another metal, such as Nickel, used. This carries additionally to an instability in the fuel cell environment further to the manufacturing costs. By using the internally assisted method of the present invention Invention, no liner is required, and it may be a small thickness of only 10-20 nm can be used, whereby the manufacturing costs can be reduced.

Furthermore, as in the 10a and 10b When using an ion assisted PVD process, a smooth and uniform coating of a metal is deposited on the substrate ( 10a ). If a smooth and uniform surface is deposited on the substrate, this will prevent corrosion. In contrast, a galvanized coating is rough and porous ( 10b ). The galvanized coating includes many peaks and valleys that do not ensure that the entire substrate is coated, which in turn leads to corrosion of the substrate. These many peaks and valleys also ensure no electrical contact in the valleys. Further, in the valleys, there may still be an oxide that can contaminate the fuel cell. This is clearer in the 11a and 11b shown.

The 11a show an atomic force microscope image of a gold plating made by the internally assisted PVD process of the present invention. As in 11a can be seen, the coating is smooth and even. A roughness analysis as well as an analysis of the range from peaks to valleys was also performed. The mean roughness (Ra) of the internally supported PVD coating was only 184.78 nm, and the peak to valley (Z) area was only 1.119 microns. The peak-to-valley range should be less than 3,000 microns, more preferably less than 2,800 microns, even more preferably less than 2,500 microns, preferably less than 2,000 microns, and most preferably less than 1,500 microns. With such a smooth and uniform surface, the coating of the present invention ensures that electrical contact between the bipolar plates is maintained. Also, the smooth and even surface ensures that any oxide that has not been completely removed by the internally assisted PVD process is completely coated and thereby prevented from contamination of the fuel cell.

In contrast, shows how in 11b An atomic force microscope image of a galvanized coating shows that the coating is rough and porous. There are many protruding tubers available. The roughness analysis as well as the peak to valley area of the galvanized coating shows an average roughness (Ra) of 415.88 nm and a range of peaks to valleys (Z) of 2.860 microns. Thus, the many peaks and valleys of the plated coating do not ensure reliable electrical contact between the bipolar plates. The galvanized coating also does not ensure that any oxides that may contaminate the fuel cell have been removed or coated.

Yet another advantage of the present invention, as described above and in the first embodiment, is the optional coating of the inner surfaces 90 and 92 the layers 58 and 60 ( 2 ) to ensure that between the layers 58 and 60 an electrical contact is maintained. Typically, the layers become 58 and 60 connected by an adhesive (not shown). However, if such an adhesive is used, a coolant that is between the layers may 58 and 60 is used to attack the adhesive and significantly increase the resistance between the layers 58 and 60 have as a consequence. By coating the inner surfaces 90 and 92 the layers 58 and 60 with the conductive coating 94 According to the present invention, the resistance between the layers 58 and 60 be kept to a minimum for longer periods of time.

This advantage of the present invention was tested by placing a bipolar plate connected by an adhesive in a bath of deionized water at 80 degrees Celsius. The bipolar plate still exhibited minimal interlayer resistance even after 5000 hours 58 and 60 on. This is a result of the coating 94 which has excellent adhesion to the adhesive as well as easing excellent electrical conductivity between the layers 58 and 60 ,

Yet another advantage of using a noble metal coating deposited via internally assisted PVD is that the compression pressure is associated with little variation in contact resistance as compared to a conventionally known coating, such as Acheson. This is in 12 shown. The samples tested were 20 nm Au, 15 nm Au and 10 nm Au on stainless steel substrates. Acheson (a conductive carbon-based coating purchased from Acheson Corp.) was coated on a titanium substrate. The contact resistance was measured by squeezing the samples between two diffusion papers from Toray. The pressures were varied between 3.45 bar to 13.8 bar (50-200 psi) while applying a current of 1 A / cm ² . The contact resistances were obtained by measuring the voltage drop between the diffusion papers and the metal samples over the coating. As in 12 10 nm, 15 nm and 20 nm gold coatings produce very low contact resistances over a wide compression range of 3.45 to 13.8 bar (50-200 psi). Specifically, the contact resistance typically has a value between 1.5 and 6.5 milliohms / cm ² with a very low percent loss over the pressure range of 3.45 to 13.8 bar (50 to 200 psi). The Acheson coating, on the other hand, had a contact resistance of between 12 and 31 milliohms / cm ² with a significant percentage loss over the pressure range of 3.45 bar to 13.8 bar (50-200 psi). The low contact resistance of the present invention allows stacking pressures used for the fuel cell stack to be lowered, which in turn prolongs the life of the stack as well as prevents fiber impingement on the MEA.

The effects of the present invention on the contact resistance as well as the cell voltage are also in 13 shown. 13 Fig. 4 is a graph showing a comparison of a 317L stainless steel substrate coated with 10 nm Au according to the present invention, a non-coated 317L stainless steel substrate and a Poco graphite substrate. As in 13 As can be seen, the electrically conductive coating of the present invention provides a significant advantage in cell voltage and contact resistance over an uncoated stainless steel substrate. Compared to a Poco graphite substrate, the electrically conductive coating of the present invention provides a cell voltage that is substantially the same is while providing a lower contact resistance. Thus, the electroconductive coating of the present invention provides an overall advantage over poco-graphite because the overall cost to produce a stainless steel substrate coated with the electroconductive coating of the present invention is low.

Another advantage of the present invention is that the conductive coating prevents passivation of the bipolar plates. As in 14 As can be seen, a stainless steel substrate coated with 10 nm Au gives only low corrosion currents when the potential is between +0.4 and +0.6 V (vs. Ag / AgCl) in a vented solution at 80 Celsius is cyclically changed, where is simulated by a bipolar plate environment in a fuel cell (pH = 3.0, 10 ppm HF and 0.5 M Na ₂ SO ₄ as carrier electrolyte).

Potentiostatic corrosion experiments were also performed over 100 hours at both +0.6 V (vs. Ag / AgCl) in air and at -0.4 V (Ag / AgCl) in hydrogen for a stainless steel substrate coated with 10 nm Au was coated, performed. As in 15 can be seen, the measured corrosion currents under these conditions were very low (below 1 uA / cm ² ), which shows good stability of the coating.

As from the foregoing detailed description, The present invention provides an ultrathin conductive coating which Made of a precious metal, which is the surface of a Substrate sufficiently covered to prevent corrosion and a low contact resistance for an electrically conductive Fluid distribution element provides that the overall performance a fuel cell improved. Furthermore, because of this, that the coating is coated with an ultra-low loading of a noble metal is the production cost of producing an electrically conductive Fluid distribution element kept to a minimum.

Claims (33)

Method for producing an electrically conductive Fluid distribution element, comprising the steps of: a substrate is provided; cleaned the substrate with an ion beam becomes; and an electrically conductive coating on the substrate deposited by PVD to a thickness of less than 100 nm, in which the cleaning and the deposition are carried out substantially simultaneously. The method of claim 1, wherein the cleaning comprises the deposition is started and the cleaning continues during the deposition becomes. The method of claim 1, further comprising the cleaning of the substrate is continued at least for so long until the deposition is finished. The method of claim 3, wherein the cleaning ends after the deposition is completed. The method of claim 1, wherein the coating is deposited to a thickness of less than 80 nm. The method of claim 1, wherein the coating has a thickness of 10 to 20 nm. The method of claim 1, wherein the electrically conductive coating is deposited to a loading of 0.02 to 0.04 mg / cm ² . The method of claim 1, wherein the substrate is made of chosen by the group which includes stainless steel, aluminum and titanium. The method of claim 1, wherein the coating a precious metal. The method of claim 9, wherein the noble metal chosen from the group is Ru, Rh, Pd, Ag, Au, Ir, Pt, Os and combinations thereof includes. The method of claim 1, wherein the coating has a contact resistance of 1.5 to 6.5 milliohms / cm ² . The method of claim 1, wherein the coating a corrosion resistant Coating includes. The method of claim 1, wherein the cleaning step comprises removing an oxide layer from the substrate. The method of claim 1, wherein the coating at a rate of 0.10 nm / sec. Electrically conductive fluid distribution element with: one Metal substrate; and an electrically conductive coating, those on a surface of the substrate which is pure of oxides, wherein the coating has a thickness of less than 80 nm. The element of claim 15, wherein the coating is delaminated from the substrate withstands when a cathodic current of over 10 mA / cm ^{2 is applied} to the element. The element of claim 15, wherein the coating a thickness of 10-20 nm has. The element of claim 17, wherein the electrically conductive coating has a loading of 0.02 to 0.04 mg / cm ² . The element of claim 15, wherein the substrate is made of a group which includes stainless steel, aluminum and titanium. The element of claim 15, wherein the coating a noble metal selected from the group consisting of Ru, Rh, Pd, Ag, Au, Ir, Pt, Os and combinations thereof. The element of claim 15, wherein the coating has a contact resistance of 1.5 to 6.5 milliohms / cm ² . The element of claim 20, wherein the noble metal is a backsheet the coating forms, and the coating further comprises an intermediate metal layer a corrosion resistant Non-precious metal is included between the substrate and the outer layer is arranged. The element of claim 15, wherein the substrate is a surface having a plurality of grooves and lands, wherein at least the webs coated with the electrically conductive coating are. The element of claim 15, wherein the coating a smooth surface which extends through a range of peaks to valleys of less than 2.5 microns. Fuel cell with a variety of electrically conductive Fluid distribution elements and with a plurality of membrane electrode assemblies, in which the membrane electrode assemblies comprise a polymer electrolyte having a Anode on a site of the membrane electrolyte and egg ner cathode comprise an opposite side of the membrane electrolyte, and wherein the element comprises: an electrically conductive Polymer substrate; and an electrically conductive metal coating, which is arranged on the substrate, the coating has a thickness of less than 100 nm. A fuel cell according to claim 25, wherein the polymer substrate a composite comprising a polymer and a conductive filler, which is distributed in the polymer comprises. The fuel cell of claim 26, wherein the conductive filler chosen from the group is the carbon fibers, graphite fibers, nickel-coated graphite fibers, Includes stainless steel fibers and combinations thereof. A fuel cell according to claim 26, wherein the polymer chosen from the group which comprises: silicone, polyisobutylene, epoxy or epoxy resin, Vinyl ester, phenol or phenolic resin, polypropylene, polytetrafluoroethylene, Nylon, rubber-modified polypropylene and their blends. A fuel cell according to claim 25, wherein the coating a noble metal selected from the group consisting of Ru, Rh, Pd, Au, Ag, Ir, Pt, Os and combinations thereof. Fuel cell with a variety of electrically conductive Fluid distribution elements and with a plurality of membrane electrode assemblies, in which the membrane electrode assemblies comprise a polymer electrolyte having a Anode on one side of the membrane electrolyte and a cathode on an opposite side of the membrane electrolyte, and wherein the element comprises: a conductive foam with outer surfaces, which are pure of oxides, and with internal openings that pass through form the foam for fluid distribution; and an electric one conductive metal coating on the outer surfaces and optionally on the inner surfaces; in which the coating has a thickness of less than 100 nm. A fuel cell according to claim 30, wherein the coating a noble metal selected from the group consisting of Ru, Rh, Pd, Ag, Au, Ir, Pt, Os and combinations thereof. A fuel cell according to claim 30, wherein the foam chosen from the group is, the stainless steel, nickel, aluminum, titanium and carbon includes. Fuel cell with a variety of electrically conductive Fluid distribution elements according to claim 15; and a variety of Membrane electrode assemblies, wherein the membrane electrode assemblies a Polymer electrolyte with an anode on one side of the membrane electrolyte and a cathode on an opposite side of the membrane electrolyte include.